High-Entropy Perovskite Oxides as a Family of Electrocatalysts for Efficient and Selective Nitrogen Oxidation

Electrocatalytic nitrogen oxidation reaction (NOR) can convert nitrogen (N₂) into nitrate (NO₃^-) under ambient conditions, providing an attractive approach for synthesis of NO₃^-, alternative to the current approach involving the harsh Haber-Bosch and Ostwald oxidation processes that necessitate high temperature, high pressure, and substantial carbon emission. Developing efficient NOR catalysts is a prerequisite, which remains a formidable challenge, owing to the weak activation/dissociation of N₂. A variety of NOR electrocatalysts have been developed, but their NOR kinetics are still extremely sluggish, resulting in inferior Faradaic Efficiencies. Here, we report a high-entropy Ru-based perovskite oxide (denoted as Ru-HEP) that can function as a high-performance NOR catalyst and exhibit a high NO₃^- yield rate of 39.0 μmol mg^-1 h^-1 with a Faradaic Efficiency of 32.8%. Both our experimental results and theoretical calculations suggest that the high-entropy configuration of Ru-HEP perovskite oxide can markedly enhance the oxygen-vacancy concentration, where the Ru sites and their neighboring oxygen vacancies can serve as unsaturated centers and decrease the overall energy barrier for N₂ electrooxidation, thereby leading to promoted NOR kinetics. This work presents an alternative avenue for promoting NOR catalysis on perovskite oxides through the high-entropy engineering strategy.